Bis[alpha-(substituted phenylthio)-p-tolyl] ethers



United States Patent The present invention is directed toblS[OL-(SUbStltlltCd phenylthio)-p-tolyl] ethers having the formula tQJT In this and succeeding formulae, R represents a member of the groupconsisting of phenyl, halophenyl, tolyl and cumenyl. In the presentspecification and claims, the halo refers to chlorine and bromine. Thecompounds of the present invention are liquids or solids which are oflow solubility in water and of moderate solubility in many organicliquids. These crystalline solid materials have been found to be usefulas pesticides for the control of worm, fungal, bacterial and insectorganisms such as cockroaches, Erysiphe cichovacearum, peas, sorgum,Edwinia amylovora, Japanese millet, rootknot nematodes, Bacillus cereusand poultry enteric disease.

The compounds of the present reaction are prepared by reacting tdgethera p,p-bis(dihalomethyl)diphenyl oxide and a substituted thiophenolhaving the formula The reaction can be conveniently carried out inexcess of the thiophenol reactant, wherein the excess thiophenol servesas reaction medium. In an alternate procedure, the reaction can beconveniently carried out in the presence of an inert organic solvent asreaction medium. The reaction proceeds smoothly at temperatures at whichthe desired product and hydrogen chloride of reaction are formed.Ordinarily, the reaction proceeds readily at temperatures between 50*and 200 C. and preferably at temperatures between 80' and 150 C. Theamounts of the reactants to be employed are not critical, some of thedesired product being formed when employing the reactant in anyproportions. However, the reaction consumes two moles of the substitutedthiophenol compound for each mole of the dihalomethyl diphenyl oxide anduse of the reactants in such proportions is preferred.

In carrying out the reaction, the p,p'-bis(dihalomethyl) diphenyl oxideand substituted thiophenol are combined in any order or fashion.Representative inert organic solvents which can be employed as reactionmedia include benzene, toluene, xylene and cyclohexane. The reactionmixture is elevated to and maintained at the reaction temperature untilthere is a substantial cessation in the formation of the hydrogen halideof reaction. Thereafter, the desired product is removed from thereaction medium 'by such conventional procedures as filtration ordistillation of the low boiling constituents to yield a product as asolid residue. This residue can be employed in pesticidal applicationsor further purified by such conventional procedures as washing with anappropriate liquid or recrystallization from a suitable solvent beforebeing employed in such applications.

The following examples are merely illustrative and are not intended tobe limiting.

3,338,976 Patented Aug. 29, 1967 Bis (a- (phenylthio) -p-t0lyl) etherp,p'bis(dichloromethyl)diphenyl oxide (40 grams; 0.15 mole) was combinedwith thiophenol (166 grams; 0.66 mole). The resulting mixture was heatedwith stirring at 12814l C. for 21 hours. Thereafter, the reactionmixture was distilled under reduced pressure to remove the unreactedthiophenol and leave the 'bis(a- (phenylthio) -p-tolyl) ether product asa solid residue. This residue was recrystallized from toluene and therecrystallized product found to melt at Ill-112 C.

Bis[a-(p-bromophenylthio) p-tolyl] ether p,p'-Bis(chloromethyl)diphenyloxide (40 grams; 0.15 mole) and p-bromothiophenol (57 grams; 0.30 mole)are dispersed with stirring in 300 milliliters of xylene. The resultingmixture is heated with stirring at 130 C. for about 30 hours. Followingthe reaction period, the reaction mixture is fractionally distilledunder reduced pressure to remove the low boiling constituents and obtainthe bis(u-(p-bromophenylthio)-p-tolyl) ether product as a crystallineresidue. This residue is recrystallized from toluene and found to meltat 1l3.5-117 C.

In similar procedures, the following compounds of the present inventionare prepared.

Bis[a-(2,3,5,6-tetrachlorophenylthio) p tolyl] ether (molecular weight689.6) by reacting together 2,3,5,6- tetrachlorothiophenol and p,p-bis(chloromethyl)diphenyl oxide.

Bis[a-(2,5-dibromophenylthio)-p-tolyl] ether (molecular weight 729.6) byreacting together 2,5-dichlorothiophenol andp,p-bis(chloromethyl)diphenyl oxide.

Bis[ot-(4-chlorophenylthio)-p-to1yl] ether (melting at 1l9-121 C.) byreacting together 4-chlorothiophenol and p,p-bis (chloromethyl)diphenyloxide.

Bis[a-(2,3-dichlorophenylthio)-p-tolyl] ether (molecular weight 551.8)by reacting 2,3-dichlorothiophenol and p,p-bis (chloromethyl diphenyloxide.

Bis[a-(p-tolylthio) -p -tolyl] ether (molecular weight 442) by reactingp-tolylthiophenol and p,p'-bis(chloromethyl)diphenyl oxide.

Bis[a-(m-tolylthio)-p-tolyl] ether (refractive index n of 1.6492) byreacting together p,p'-bis(chloromethyl)diphenyl oxide andm-tolylthiophenol.

Bis[a (m cumenylthio)-p-tolyl] ether (molecular weight 498) by reactingtogether m-cumenyl-t-hiophenol and p,p'-'bis(chlo-romethyl)diphenyloxide.

Bis[a-(o-cumenylthio)-p-tolyl] ether refractive index 11 of 1.6218) byreacting together o-cumenylthiophenol and p,p-bis(chloromethyl)diphenyloxide.

BiS[m (p cumenylthio) p-tolyl] ether (molecular weight 498) by reactingtogether p-cumenylthiophenol and p,p'-bis-(chloromethyl)diphenyl oxide.

Bis[a-(o-tolylthio)-p-tolyl] ether (molecular weight 442) :by reactingtogether o-tolylthiiophenol and p,p-bis (chloromethyl)diphenyl oxide.

Bis[a (pentachlorophenylthio) p-tolyl] ether (molecular weight 758.5) byreacting together pentachlorothiophenol and p,p'-bis(chloromethyl)diphenyl oxide.

The compounds of the present invention are useful as pesticides for thecontrol of rnany fungal, bacterial and insect pests. For such use, theunmodified compounds can be used. Alternatively, the compounds can beadapted to be dispersed in or on various environments such as soil,plant parts, textiles, paper, wood, etc. In such adaptations thetoxic-ant compound is dispersed on finely divided solids and theresulting preparation employed as a dust. Also, such preparations can bedispersed in water without the aid of a wetting agent and the resultingaqueous dispersions employed as sprays. In other procedures, thecompound can be employed in oil or in other solvent, or as a constituentor solvent-in-water or waterin-solvent emulsions or as aqueousdispersions thereof which can be applied as a spray, drench or wash.

In representative operations, aqueous compositions containingbis[a-(4-bromophenylthio)-p-tolyl] ether at concentrations of 500 partsper million by weight give complete kills of Edwinz'a wmylovora(bacterium fire blight) and Bacillus cereus. In further operations,aqueous compositions containing bis[a-(3-tolylthio)-p-toly1] ether at aconcentration of 5000 parts per million by weight give substantiallycomplete kills of Erysiphe cichovaceawm (powdery mildew). In otheroperations, aqueous compositions containingbis[u-(4-chlorophenylthio)-p-tolyl] ether at concentrations of 100pounds per acre give substantially complete kills of peas and sorgum.

I claim:

1. A compound corresponding to the formula wherein R represents a memberof the group consisting of phenyl, halophenyl wherein halo is chlorineor bromine, tolyl and cumenyl.

2. Bis[u-(4-bromophenylthio)-p-tolyl] ether.

3, Bis[a-(4-chlorophenylthio)-p-tolyl] ether.

4. Bis [a- 3-tolylthio -p-toly1] ether.

5. Bis[a-(2,5-dibrom0phenylthio)-p-tolyl] ether.

No references cited.

CHARLES B. PARKER, Primary Examiner.

DELBERT R. PHILLIPS, Assistant Examiner.

1. A COMPOUND CORRESPONDING TO THE FORMULA